TWI393728B - Monomers, oligomers and polymers of thieno[2,3-b]thiophene - Google Patents

Abstract

The invention relates to novel mono-, oligo and polymers of thieno[2,3-b]thiophene, to their use as semiconductors or charge transport materials, in optical, electro-optical or electronic devices like LCDs, optical films, FETs or OFETs for TFT-LCDs and IC devices such as RFID tags, electroluminescent devices in flat panel displays or photovoltaic or sensor devices, and further relates to a FET, light emitting device or ID tag comprising the novel polymers.

Description

Monomers, oligomers and polymers of thieno[2,3-b]thiophenes

This invention relates to novel monomers, oligomers and polymers of thieno[3,2-b]thiophenes. The invention further relates to optical, optoelectronic or electronic devices (eg, liquid crystal displays, optical films, organic field transistors (FETs or OFETs) for thin film transistor liquid crystal displays, and integrated circuit devices (eg, RFID tags) The use as a semiconductor or charge transfer material in electroluminescent devices in flat panel displays, and in photovoltaic devices and sensor devices. The invention further relates to a field effect transistor, illuminating device or ID tag comprising such novel polymers.

Recently, organic materials have been shown to be useful as organic-based thin film transistors and active layers in organic field-effect transistors [see HEKatz, Z. Bao and SLGilat, Acc. Chem. Res., 2001, 34, 5,359]. These devices have potential applications in switching elements in smart cards, security tags and flat panel displays. If the organic material can be precipitated from the solution, it can be inferred that it has a significant cost advantage over its hydrazine analog, as this is a fast, large-area manufacturing route.

The performance of the device is mainly based on the charge carrier mobility and current on/off ratio of the semiconductor material. Therefore, the ideal semiconductor should have a low conductivity in the off state and have a high charge carrier migration. Rate (>1 x 10 ^{- 3} cm ² V ^{- 1} s ^{- 1} ). In addition, it is important that the semiconductor material is relatively stable to oxidation, that is, it should have a high ionization potential, which may result in a decrease in device performance due to oxidation.

Head has been reported with the position regularity - tail poly (3-hexylthiophene) having from 1 x 10 ^{- 5} to ^{4.5 x 10 - 2 cm 2 V} - 1 s - charge carrier mobility of ^1, but with a A relatively low current on/off ratio from 10 to 10 ³ [see Z. Bao et al., Appl. Pys. Lett., 1996, 69, 4108]. This current on/off ratio is due in part to the low ionization potential of the polymer, which can result in oxygen doping of the polymer under ambient conditions, and a subsequent high breaking current [see H. Sirringhaus Et al., Adv. Solid State Phys., 1999, 39, 101].

High positional regularity results in improved encapsulation and optimized microstructure resulting in improved charge carrier mobility [see H. Sirringhaus et al, Science, 1998, 280, 1741-1744; H. Sirringhaus et al. , Nature, 1999, 401, 685-688; and H. Sirringhaus et al., Synthetic Metals, 2000, 111-112, 129-132]. In general, poly(3-alkylthiophenes) can exhibit improved solubility and can be solution treated to produce large area films. However, poly(3-alkylthiophenes) have a relatively low ionization potential and are easily doped in air.

It is an object of the present invention to provide novel materials useful as semiconductor or charge transport materials that are susceptible to synthesis, have high charge mobility, good handleability, and oxidative stability.

Another object of the present invention is to provide novel semiconductor and charge transfer devices, and novel and improved optoelectronic, electronic, and electroluminescent devices comprising the same, for example, as integrated circuit components or thin film transistor (TFT) components. Field effect transistors (FETs), and organic light emitting diode (OLED) applications, such as backlights for electroluminescent displays or liquid crystal displays.

Other objects of the invention will become apparent to those skilled in the art from this description.

The inventors of the present invention have found that such objects can be achieved by providing monomers, oligomers and polymers of thieno[2,3-b]thiophenes as claimed in the present invention.

G.Ko Mehl et al, Makromol. Chem. 1982, 183, 2747-2769 discloses poly(thieno[2,3-b]thiophene-2,5-di-extended vinyl extended aryl) and methods for preparing the same from aldehyde monomers However, the compounds of the invention are not disclosed.

The present invention relates to monomeric, oligomeric and polymeric compounds of formula I Wherein R ¹ and R ² are each independently H; halogen; optionally substituted aryl or heteroaryl; P-Sp-; P ^* -Sp-; or a linear chain having from 1 to 20 C atoms Branched or cycloalkyl, which may be unsubstituted, mono- or polysubstituted by F, Cl, Br, I or CN, wherein one or more non-adjacent CH ₂ groups may also be independently of each other in each case By -O-, -S-, -NH-, -NR ⁰ -, -SiR ⁰ R ^{0 0} -, -CO-, -COO-, -OCO-, -O-CO-O-, -S-CO -, -CO-S-, -CX ¹ =CX ² - or -C≡C-substitution, but in such a way that the O and/or S atoms are not directly linked to each other, and R ³ and R ⁴ have R independently of each other. ^One of the meanings of ¹ or represents -Sn(R ⁰ ) ₃ , -B(OR')(OR"), -CH ₂ Cl, -CHO, -CH=CH ₂ or -SiR ⁰ R ^{0 0} R ^{0 0 0} , R ⁰ , R ^{0 0} , R ^{0 0 0} are each independently H, an aryl group or an alkyl group having 1 to 12 C atoms, and R' and R" are independently H or have 1 to 12 C atoms. alkyl, or oR 'and oR "together with the boron atom form a cyclic group having 2 to 20 C atoms, X ¹ and X ² are each independently based H, F, Cl CN, P based a polymerizable group, P ^* can be converted into a ^line a polymerizable group P or group may be substituted by, Sp based a spacer group or a single bond, n lines a An integer of 1, wherein the repeating units may be the same or different, and when n is 1 and R ¹ and R ² are H, one or both of R ³ and R ⁴ are P-Sp-, halogen, -Sn (R ⁰ ) ₃ , -B(OR')(OR"), -CH ₂ Cl, -CH=CH ₂ , -SiR ⁰ R ^{0 0} R ^{0 0 0} .

The invention further relates to a semiconducting, electroluminescent or charge transporting material, component or device comprising at least one compound as defined above and below.

The invention further relates to the use of the compounds according to the invention as semiconductor or charge transport materials, in particular in optical, optoelectronic or electronic devices, for example in field effect transistors (FETs) as components of integrated circuits, as films The transistor is used in flat panel display applications (such as liquid crystal displays (LCDs)) for radio frequency identification (RFID) tags, or for displays or organic light emitting diodes (OLEDs) (including both charge transfer layers and electroluminescent layers) ) in the semiconductor component.

The invention further relates to the use of the compounds of the invention as electroluminescent materials, which can be used in OLED applications (for example as backlights for electroluminescent displays or displays), in photovoltaic devices or in sensor devices, Used as an electrode material in batteries, as a photoconductor, in electrophotographic applications (such as electrophotographic recording), in organic memory devices, for detecting and judging DNA sequences and as an LCD or OLED device Alignment layer.

The invention further relates to an optical, optoelectronic or electronic device, FET, integrated circuit (IC), TFT, OLED or alignment layer comprising a semiconducting or charge transporting material, component or device of the invention.

The invention further relates to a flat panel display TFT or TFT array, radio frequency identification (RFID) tag, electroluminescent display or backlight comprising the semiconducting or charge transfer material, component or device of the invention or a FET, IC, TFT or OLED .

The invention further relates to a security tag or device comprising the FET or RFID tag of the invention.

Formula I encompasses monomers, oligomers, and polymers of thieno[2,3-b]thiophenes. The polymers may be homopolymers, i.e., copolymers having the same repeating unit or having different repeating units of formula I. Particularly preferred are the homopolymers of formula I which comprise the same repeating unit.

Particularly preferred is a 3-position substituted poly(thieno[2,3-b]thiophene), especially a 3-methyl-substituted poly(thiophene[2,3-b] ]thiophene). This material can be considered as an analog of poly(3-alkylthiophene) which exhibits extremely high charge carrier mobility when positional regularity is high (>96%) and is therefore suitable for use in semiconductor devices (eg In the transistor). Polymers with high positional regularity can self-organize into well-ordered sheet-like films that can result in high charge carrier mobility.

However, a disadvantage of a PAT is that it has only limited air stability, which can result in high disconnect current and loss of a transistor characteristic when the device is operated in air without a suitable oxygen barrier. The oxygen doping of the material is related to the low ionization potential of the conjugated polymer.

In comparison, the polymers of the present invention are capable of self-organizing into a well-packaged structure to maintain desirable high charge carrier mobility and can be significantly improved by reducing ionization potential and preventing oxygen doping. The air stability of the material. Since the thieno[2,3]thiophene units cannot form a delocalized quino-type resonance structure with adjacent aromatic units, the polymers exhibit higher air stability. This can limit the effective conjugation length of the polymers, thereby reducing HOMO levels and increasing the ionization potential.

Therefore, the compounds of the present invention are especially useful as charge transfer semiconductors. The introduction of an alkyl side chain into the thienothiophene group further improves the solubility and solution treatability of the polymers.

More particularly preferred are compounds of formula I wherein: -n is an integer from 2 to 5,000, preferably from 10 to 5,000, most preferably from 100 to 1000, and the molecular weight (Mw) is from 5,000 to 300,000, particularly from 20,000. to 100,000, n lines ^1, -R 1 or R ² lines H, -R ¹ and R ² is different from H, -R ¹ identical with R ^2, -R ¹ and R ² lines H, and the other selected from the group From C ₁ -C _{2 0} -alkyl, C ₁ -C _{2 0} -alkoxy, C ₁ -C _{2 0} -alkenyl, C ₁ -C _{2 0} -alkynyl, C ₁ -C _{2 0} -alkane Thio group, C ₁ -C _{2 0} -forminyl group, C ₁ -C _{2 0} -ester, C ₁ -C _{2 0} -amino group, C ₁ -C _{2 0} -fluoroalkyl group, and optionally substituted Aryl or heteroaryl, very preferably C ₁ -C _{2 0} -alkyl or C ₁ -C _{2 0} -fluoroalkyl, -R ¹ and R ² are selected from C ₁ -C _{2 0} - Alkyl, C ₁ -C _{2 0} -alkoxy, C ₁ -C _{2 0} -alkenyl, C ₁ -C _{2 0} -alkynyl, C ₁ -C _{2 0} -alkylthio, C ₁ -C _{2 0} -carbyl, C ₁ -C _{2 0} -ester, C ₁ -C _{2 0} -amino, C ₁ -C _{2 0} -fluoroalkyl, and optionally substituted aryl or heteroaryl, very good donor line C ₁ -C _{2 0} - alkoxy Or C ₁ -C _{2 0} - fluoroalkyl group, -R ¹ and one or both of R ² are selected from 4 to 20, preferably an alkyl or fluoroalkyl group with 6 to 15 C atoms, -P ^* is -OH or -O-Si-R ⁰ R ^{0 0} R ^{0 0 0} , preferably, wherein R ⁰ , R ^{0 0} and R ^{0 0 0} are selected from aryl or C _{1 - 1 2} - The same or different groups of the alkyl group, preferably a C ₁ -C ₆ -alkyl group, for example, methyl, ethyl, isopropyl, tert-butyl or phenyl, -R ³ and R ⁴ are selected From H, halogen, Sn(R ⁰ ) ₃ , B(OR')(OR"), CH ₂ Cl, CHO, CH=CH ₂ , SiR ⁰ R ^{0 0} R ^{0 0 0} and optionally substituted aryl Or a heteroaryl group, -n is 1 and one or both of R ³ and R ⁴ are preferably a halogen of Br, Cl or I, Sn(R ⁰ ) ₃ , B(OR')(OR") , CH ₂ Cl, CHO, CH=CH ₂ or SiR ⁰ R ^{0 0} R ^{0 0 0} , - at least one of R ¹ , R ² , R ³ and R ⁴ is P-Sp-, -n is 1 and R ³ And one or both of R ⁴ are P-Sp- or P ^* -Sp-.

Further preferred is a high percentage of the head-tail (HT) coupled positional regular polymer of formula I1.

The positional regularity in the polymer of the present invention is preferably at least 90%, more preferably 95% or more, very preferably 98% or more, and most preferably from 99 to 100%.

Positionally regular polymers are advantageous because they exhibit strong interchain π-π-stack interactions and a high degree of crystallinity, making them an effective charge transport material with high carrier mobility.

Further preferred are liquid crystal precursors or liquid crystal monomers, oligomers and polymers, in particular polymers which form a rod phase and formula I which comprise one or more P-Sp-groups and form a rod-like phase. Polymerization of monomers.

Very good for the following polymers Wherein R ^{1 - 4} independently of one another has one of the meanings of formula I different from hydrogen, n is as defined in formula I, and m is n/2.

When R ^{1 -} one of the ^four lines aryl or heteroaryl group, it is preferably one containing up to 25 C atoms mono -, bis -, or tricyclic aryl or heteroaryl, wherein such rings may be fused system Healing. The heteroaryl group contains at least one hetero ring atom preferably selected from the group consisting of N, O and S. The aryl or heteroaryl groups are optionally substituted with one or more groups L.

L series F, Cl, Br, I, CN or a linear alkyl group having 1 to 20 C atoms, a branched alkyl group or a cycloalkyl group, such a linear alkyl group, a branched alkyl group or a naphthenic group The group may be unsubstituted, mono- or polysubstituted by F, Cl, Br, I, -CN or -OH, and wherein one or more of the non-adjacent CH ₂ groups are in each case independent of each other as appropriate - O-, -S-, -NH-, -NR ⁰ -, -SiR ⁰ R ^{0 0} -, -CO-, -COO-, OCO-, -OCO-O, -S-CO-, -CO-S -, -CH=CH- or -C≡C-substitution, and the substitution requires that the O and/or S atoms are not directly connected to each other.

Eugenyl and heteroaryl phenyl, fluorinated phenyl, pyridine, pyrimidine, diphenyl, naphthalene, optionally fluorinated or alkylated or fluoroalkylated benzo[1,2-b : 4,5-b']dithiophene, fluorinated or alkylated or fluoroalkylated thieno[3,2-b]thiophene, optionally fluorinated or alkylated or fluoroalkane The grouped 2,2-dithiophene, thiazole and oxazole, all of which are unsubstituted, are singly or polysubstituted as defined above.

When R ^{1 -} one ⁴ alkyl or alkoxy-based, i.e., when the terminal CH ₂ group represented by -O- Alternatively, it may be based straight or branched chain group. It is preferably a linear group having 2 to 8 carbon atoms, and thus is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy. , butoxy, pentyloxy, hexyloxy, heptyloxy, or octyloxy, which may also be, for example, methyl, decyl, decyl, undecyl, dodecyl, thirteen Alkyl, tetradecyl, pentadecyl, anthracenyloxy, nonyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

The fluoroalkyl or fluorinated alkyl or alkoxy group is preferably a linear (O)C _i F _{2 i + 1} wherein i is an integer from 1 to 20, especially from 1 to 15, an integer The best is (O)CF ₃ , (O)C ₂ F ₅ , (O)C ₃ F ₇ , (O)C ₄ F ₉ , (O)C ₅ F _{1 1} , (O)C ₆ F _{1 3} (O)C ₇ F _{1 5} or (O)C ₈ F _{1 7} , the best system (O)C ₆ F _{1 3} .

CX ¹ =CX ^{2 is} preferably -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -CH=C(CN)- or -C(CN)=CH-.

The halogen is preferably F, Br or Cl.

The hetero atom is preferably selected from the group consisting of N, O and S.

The polymerizable group P can participate in a polymerization reaction (for example, radical or ionic chain polymerization, addition polymerization or polycondensation) or can be grafted to a similar polymerization reaction by, for example, a condensation or addition reaction. a group on a polymer backbone. Particularly preferred are polymerizable groups for chain polymerization (e.g., free radical, cationic or anionic polymerization). An excellent one is a polymerizable group containing a C-C double bond or a triple bond and a polymerizable group which can be polymerized by a ring opening reaction, such as propylene oxide or an epoxide.

The polymerizable group P is preferably selected from the group consisting of CH ₂ =CW ¹ -COO-, , , CH ₂ =CW ² -(O) _{k 1} -,CH ₃ -CH=CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, (CH ₂ =CH-CH ₂ ) ₂ CH-OCO-, (CH ₂ =CH-CH ₂ ) ₂ N-, HO-CW ² W ³ -, HS-CW ² W ³ -, HW ² N-, HO-CW ² W ³ -NH-, CH ₂ =CW ¹ -CO-NH-, CH ₂ =CH-(COO) _{k 1} -Phe-(O) _{k 2} -, Phe-CH=CH-, HOOC-, OCN- And W ⁴ W ⁵ W ⁶ Si-, wherein W ¹ is H, Cl, CN, phenyl or an alkyl group having 1 to 5 carbon atoms, especially H, Cl or CH ₃ ; W ² and W ³ are mutually Independently H or an alkyl group having 1 to 5 carbon atoms, especially methyl, ethyl or n-propyl; W ⁴ , W ⁵ and W ⁶ are independently of each other, Cl, having 1 to 5 C atoms Oxoalkyl or oxacarbonylalkyl; Phe is 1,4-phenyl, and k ₁ and k ₂ are independently 0 or 1 independently of each other.

The group P is CH ₂ =CH-COO-, CH ₂ =C(CH ₃ )-COO-, CH ₂ =CH-, CH ₂ =CH-O-, (CH ₂ =CH) ₂ CH-OCO -, (CH ₂ =CH) ₂ CH-O-, and .

Excellent are acrylate and propylene oxide based. Propylene oxide causes less shrinkage during polymerization (crosslinking), which creates less stress in the film and thus retains higher order and less defects. Crosslinking of propylene oxide also requires a cationic initiator which, unlike the free radical initiator, is inert to oxygen.

As far as the spacer group Sp is concerned, all groups known to the person skilled in the art to be used for this purpose can be used. The spacer group Sp preferably has the formula Sp'-X, thus the P-Sp-line P-Sp'-X-, and the P ^* -Sp-line P ^* -Sp'-X-, wherein the Sp' system has up to An alkyl group of 20 C atoms which may be unsubstituted or mono- or poly-substituted by F, Cl, Br, I or CN, wherein one or more non-adjacent CH ₂ groups may also be used in each case Independently from -O-, -S-, -NH-, -NR ⁰ -, -SiR ⁰ R ^{0 0} -, -CO-, -COO-, -OCO-, -OCO-O-, -S- CO-, -CO-S-, -CH=CH- or -C≡C- substitution, the alternative is that O and / or S atoms are not directly connected to each other, X-series -O-, -S-, -CO- , -COO-, -OCO-, -O-COO-, -CO-NR ⁰ -, -NR ⁰ -CO-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S- , -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰ -, -CX ¹ =CX ² -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or one single bond, ^{R 0, R 0 0, X} 1 and X ² have the above meanings given one.

X is preferably -O-, -S-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S- , -SCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N -, -CH=CR ⁰ -, -CX ¹ =CX ² -, -C≡C- or a single bond, especially -O-, -S-, -C≡C-, -CX ¹ =CX ² - Or a single bond, which is a group which forms a conjugated system, such as -C≡C- or -CX ¹ =CX ² -, or a single bond.

Typical examples of the Sp' group are -(CH ₂ ) _p -, -(CH ₂ CH ₂ O) _q -CH ₂ CH ₂ -, -CH ₂ CH ₂ -S-CH ₂ CH ₂ - or -CH ₂ CH ₂ —NH—CH ₂ CH ₂ — or —(SiR ⁰ R ^{0 0} —O) _p —, wherein p is an integer from 2 to 12, q is an integer from 1 to 3, and R ⁰ and R ^{0 0} has the meaning given above.

Preferred Sp' groups are, for example, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, and undecane. Base, dodecyl, octadecyl, ethyl ethoxyethyl, methyleneoxy butyl, ethyl thio-ethyl, ethyl ethyl-N-methyl-imine Base ethyl, 1-methylalkyl, vinyl, propylene and butenyl.

Further preferred are compounds comprising one or two P-Sp- or P ^* -Sp- groups, wherein Sp is a single bond.

When respectively a compound comprising two P-Sp or P ^* -Sp- groups, each P or P ^* group and the Sp spacer group may be the same or different.

Another preferred embodiment relates to a compound comprising one or more P ^* -Sp- groups, wherein P ^* is a group which can be converted into a polymerizable group P as defined above or substituted therewith. Preferably, P ^* is a group having, for example, a lower spontaneous polymerization activity than a P group. Such compounds may, for example, be used as intermediates in the synthesis of polymerizable compounds of formula I1 comprising one or more P groups, or as a precursor material of a polymerizable compound that is too active to be stored or transported for extended periods of time. The P ^* group is preferably selected such that it can be readily converted to or substituted by a P group by known methods. For example, it can be a protected form of a P group. Further preferred P ^* groups are, for example, -OH or germyl, for example -O-Si-R ⁰ R ^{0 0} R ^{0 0 0} , for example, -O-Si(CH ₃ ) ₃ , -O -Si-(isopropyl) ₃ , -O-Si-(phenyl) ₃ , -O-Si-(CH ₃ ) ₂ (phenyl), -O-Si(CH ₃ ) ₂ (third-but Base or the like, which can be reacted to form, for example, a polymerizable (meth) acrylate end group.

The SCLCP obtained from the compound or mixture of the present invention by polymerization or copolymerization has a skeleton formed of a polymerizable group P.

The monomers, oligomers and polymers of the present invention can be synthesized according to known methods or by methods analogous to known methods. Some preferred methods are explained below.

The thiophene dithiol can be readily alkylated with 1-chloro-2-dodecanone according to the procedure of C. Mahatesekake (Phosphorus, Sulfur and Silicon, 1990, 47, p35). The resulting ketone can be easily cyclized to 2-alkyl-thieno[2,3-b]thiophene in chlorobenzene by treatment with an acid catalyst (amberlyst 15). The resulting monomer is monobrominated or dibrominated in THF by treatment with one or two equivalents of N-bromosuccinimide (NBS) (reaction Figure 1).

The polymerization into a polymer having positional regularity is exemplified by one of the following five methods. According to the first method, the 2-bromo-3-alkylthieno[2,3-b]thiophene is first lithiated at the 5th position by treatment with a strong base such as LDA to form a lithium salt. The lithium salt can be converted to an organozinc reagent by treatment with anhydrous zinc chloride, and the intermediate can be polymerized in situ by the addition of a bidentate nickel catalyst (similar to RDMc Cullough et al. at J. Org. Chem., A method for thiophene derivatives is disclosed in 1993, 58,904).

According to the second method, 2,5-dibromo-3-alkyl-thieno[2,3-b]thiophene is converted into an organozinc derivative by treatment with activated zinc, and the material can be borrowed. Polymerization was carried out by the addition of a bidentate nickel catalyst (similar to T.-A. Chen, RDRieke, J. Am. Chem. Soc., 1992, 114, 10087).

According to the third method, 2,5-dibromo-3-alkyl-thieno[2,3-b]thiophene is treated with one equivalent of Grignard reagent to form a single Grignard reagent. Repolymerization by addition of a nickel catalyst (similar to SMK Robert S. Loewe and; RDMc Cullough ^{*, described} in Adv. Mater., 1999, 11, 250).

According to the fourth method (Reaction Figure 2), 2-bromo-3-alkyl-thieno[2,3-b]thiophene is lithiation at the 5-position by treatment with a strong base such as LDA. A lithium salt is formed. The lithium salt is converted to an organotin reagent by treatment with trialkyltin chloride, which can be separated and purified by chromatography. This intermediate can then be obtained by treating this intermediate with a transition metal catalyst such as Pd(PPh ₃ ) ₄ (similar to that described in A. Iragi, GW Barker, J. Mater. Chem., 1998, 8, 25). .

According to the fifth method (Reaction Scheme 2), 2-bromo-3-alkyl-thieno[2,3-b]thiophene is subjected to treatment at the 5th position by treatment with a strong base such as LDA. Lithiation to form a lithium salt. The lithium salt is converted to an organoboron reagent by treatment with a suitable trialkoxy boron reagent which can be separated and purified by chromatography. Subsequent treatment of this intermediate with a transition metal catalyst such as Pd(PPh ₃ ) ₄ and a base such as CsF or aqueous potassium carbonate provides the product (similar to S. Guillerez, G. Bidan, Synth. Metals, Said in 1998, 93, 123).

As shown in the reaction scheme 3, 3,4-dialkyl-thieno[2,3-b]thiophene can be conveniently synthesized from thieno[2,3-b]thiophene in three steps. Thieno[2,3-b]thiophene is tetrabrominated by treatment with 4 equivalents of bromine dissolved in glacial acetic acid. Reduction with zinc in acetic acid removes the bromine substituent at the 2,5-position. The resulting 3,4-dibromothieno[2,3-]thiophene can be readily alkylated by various zinc reagents by treatment with an organozinc halide in the presence of a transition metal catalyst. The resulting monomer can be chemically polymerized by treatment with iron (III) chloride to obtain a homopolymer. Alternatively, bromination can be used as a component of 2,5-dibromo-3,4-dialkylthieno[2,3-b]thiophene in a copolymerization. Thus, the copolymer can be obtained by reacting with 2,5-bis(trimethylstannyl)thieno[2,3-b]thiophene in the presence of a palladium catalyst.

Another aspect of the invention pertains to both oxidized and reduced forms of the compounds and materials of the invention. Loss or acquisition of electrons results in the formation of a highly delocalized ion form with a high conductance. This can occur when exposed to common dopants. Suitable dopants and doping methods are known to those skilled in the art and are known, for example, from European Patent No. 0 528 662, U.S. Patent No. 5,198,153, or WO 96/21,659.

The doping process generally means the use of an oxidation or reducing agent in the redox reaction to treat the semiconductor material to form a delocalized ion center in the material while obtaining the corresponding counterion from the dopant used. Suitable doping methods include, for example, exposure to a doping vapor at atmospheric pressure or low pressure, electrochemical doping in a solution containing a dopant, and a dopant and pseudo-thermally diffused semiconductor material Contacting, and implanting the dopant ions into the semiconductor material.

When electrons are used as carriers, suitable dopants are, for example, halogen (eg, I ₂ , Cl ₂ , Br ₂ , ICl, ICl ₃ , IBr, and IF), Lewis acid (eg, PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , SbCl ₅ , BBr ₃ and SO ₃ ), protonic acid, organic acid, or amino acid (eg HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H and ClSO ₃ H), transition metal compounds (for example, FeCl ₃ , FeOCl, Fe(ClO ₄ ) ₃ , Fe(4-CH ₃ C ₆ H ₄ SO ₃ ) ₃ , TiCl ₄ , ZrCl ₄ , HfCl _{4 , NbF 5, NbCl 5, TaCl} 5, MoF 5, MoCl 5, WF 5, WCl 6, UF 6 and LnCl ₃ (wherein Ln lines a lanthanoid), anions ^{(e.g., Cl -, Br -, I} -, I ₃ ^- , HSO ₄ ^- , SO ₄ ^{2 -} , NO ₃ ^- , ClO ₄ ^- , BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , FeCl ₄ ^- , Fe(CN) ₆ ^{3 -} , and Various sulfonic acid anions, such as aryl-SO ₃ -). When a hole is used as a carrier, examples of dopants are cations (for example, H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ^{+ ,} and Cs) ^+), alkali metals (e.g., Li, Na, K, Rb , and Cs), alkaline earth metal (E.g., Ca, Sr, and _{Ba), O 2, XeOF 4} , (NO 2 +) (SbF 6 -), (NO 2 +) (SbCl 6 -), (NO 2 +) (BF 4 -), AgClO ₄ , H ₂ IrCl ₆ , La(NO ₃ ) ₃ , 6H ₂ O, FSO ₂ OOSO ₂ F, Eu, acetylcholine, R ₄ N ⁺ (R-alkyl group), R ₄ P ⁺ (R is an alkyl group), R ₆ As ⁺ (R is a monoalkyl group), and R ₃ S ⁺ (R is a monoalkyl group).

The conductive forms of the compounds and materials of the present invention can be used as an organic "metal" for a variety of applications such as, but not limited to, charge injection layers and ITO planarization layers in organic light-emitting diode applications, flat panel displays, and touch screen films. , an antistatic film, printed conductive substrates, patterns or traces in electronic applications such as printed circuit boards and capacitors.

A preferred embodiment of the invention is directed to monomers, oligomers and polymers having liquid crystallinity or liquid crystals of the formula I and its preferred subtypes, and very preferably one or more polymerizable groups. Very good materials of this type are monomers and oligomers of formula I and its preferred subformulae (wherein n is an integer from 1 to 15 and R ³ and/or R ⁴ represents P-Sp-).

These materials are particularly suitable for use as semiconductor or charge transport materials because they can be arranged in a uniform and highly ordered orientation in their liquid crystal phase by known techniques, thereby exhibiting a highly ordered state, thereby achieving special High charge carrier mobility. The highly ordered liquid crystal state can be fixed by in-situ polymerization or cross-linking with a P group to produce a polymer film having high charge carrier mobility and high thermal stability, high mechanical stability, and high chemical stability.

For example, if a device is made from a polymerizable liquid crystal material by in-situ polymerization, the liquid crystal material preferably comprises one or more of formula I and its preferred formula (wherein one or both of R ³ and R ⁴ All represent monomers or oligomers of P-Sp-). If a liquid crystal polymer is first produced, for example, by polymerization in a solution, and the isolated polymer is used to make the device, the polymer preferably comprises one or more Formula I and its A liquid crystal material of a monomer or oligomer of a good formula (wherein one of R ³ and R ⁴ represents P-Sp-) is prepared.

The polymerizable monomers, oligomers, and polymers of the present invention may also be copolymerized with other polymerizable liquid crystal precursors or liquid crystal monomers known in the prior art to initiate or enhance liquid crystal phase characteristics.

Thus, another aspect of the invention relates to a monomer, oligomer or polymer (which comprises at least one polymerizable group) of one or more of the invention as described above and below, and optionally comprises one or A polymerizable liquid crystal material of a plurality of additional polymerizable compounds, wherein at least one of the polymerizable monomers, oligomers, and polymers and/or additional polymerizable compounds of the present invention is liquid crystalline or liquid crystal.

Particularly preferred are liquid crystal materials having a one-phase phase and/or a smectic phase. Layered materials are especially preferred for FET applications. For OLED applications, nematic or stratified materials are preferred.

Another aspect of the invention relates to an anisotropic polymer film having charge transfer characteristics obtainable from the above polymerizable liquid crystal material, wherein the polymerizable liquid crystal material is arranged in a macroscopically uniform orientation in its liquid crystal phase and Polymerization or crosslinking to fix the orientation state.

Preferably, the polymerization is carried out as an in situ polymerization of the material through the coating layer during fabrication of the electronic or optical device comprising the semiconductor material of the present invention. When it is a liquid crystal material, the materials are preferably arranged in a vertical orientation in the liquid crystal state before polymerization, wherein the conjugated π-electron systems are perpendicular to the charge transfer direction. This ensures minimization of the molecular spacing and thus minimizes the energy required to subsequently transfer the charges between molecules. The molecules are then polymerized or crosslinked to immobilize the uniform orientation of the liquid crystal state. The alignment and curing are carried out in the liquid phase or intermediate phase of the material. This technique is well known in the art and is generally illustrated, for example, in D. J. Broer et al., Angew. Makromol. Chem. 183, (1990), 45-66.

The alignment of the liquid crystal material can be performed, for example, by processing a substrate on which the material is coated, by shearing the material during or after coating, by applying a magnetic or electric field to the coated material, or by It is achieved by adding a surface active compound to the liquid crystal material. For an overview of alignment techniques, see, for example, I. Sage in "Thermotropic Liquid Crystals" (edited by GWGray, John Wiley & Sons, 1987, pp. 75-77) and T. Uchida and H. Seki As described in "Liquid Crystals-Applications and Uses, Vol. 3", (edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pp. 1-63). For a review of alignment materials and techniques, see J. Cognard (Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pp. 1-77).

Polymerization can occur by exposure to heat or actinic radiation. Actinic radiation refers to irradiation with light such as UV light, IR light or visible light, irradiation with X-rays or γ-rays or irradiation with high-energy particles such as ions or electrons. Preferably, the polymerization is carried out by UV irradiation at a non-absorptive wavelength. For example, a single UV lamp or a group of UV lamps can be used as a source of actinic radiation. When a high light power is used, the curing time can be reduced. Another available source of actinic radiation is a laser, such as a UV laser, an IR laser, or a visible laser.

The polymerization is preferably carried out in the presence of an initiator which is absorbable at the wavelength of actinic radiation. For example, when polymerizing by means of UV light, a photoinitiator which decomposes under UV irradiation to generate radicals or ions which initiate the polymerization can be used. When curing a polymerizable material having an acrylate group or a methacrylate group, it is preferred to use a radical photoinitiator, when curing a polymerizable material having a vinyl group, an epoxy group, and an propylene oxide group, It is preferred to use a cationic sensitizer. It is also possible to use a polymerization initiator which decomposes upon heating to generate radicals or ions which initiate polymerization. As the photoinitiator for radical polymerization, for example, commercially available Irgacure 651, Irgacure 184, Darocure 1173 or Darocure 4205 (all available from Ciba Geigy AG) can be used, and for cationic photopolymerization, commercially available UVI can be used. 6974 (Union Carbide).

The polymerizable material may additionally comprise one or more other suitable components, for example, catalysts, sensitizers, stabilizers, inhibitors, chain transfer agents, co-reacting monomers, surface active compounds, lubricants, wetting agents, dispersions Agents, hydrophobic agents, binders, flow improvers, defoamers, deaerators, diluents, reactive diluents, auxiliaries, colorants, dyes or pigments.

Monomers, oligomers, and copolymers comprising one or more P-Sp- groups can also be copolymerized with the polymerizable liquid crystal precursor to initiate or enhance liquid crystal phase characteristics. Polymerizable liquid crystal precursors suitable for use as comonomers are known in the art and are disclosed in, for example, WO 93/22397; European Patent No. 0,261,712; German Patent No. 195,04,224; WO 95/22586 and WO 97/00600.

Another aspect of the invention pertains to a liquid crystal side chain polymer (SCLCP) obtained from a polymerizable liquid crystal material as defined above by polymerization or similar polymerization. Particularly preferred are monomers derived from one or more of Formula I1 and preferred embodiments thereof, wherein one or both of R ³ and R ⁴ (preferably both) are a polymerizable or reactive group. Or obtained from a SCLCP comprising one or more polymerizable mixtures of such monomers.

Another aspect of the invention pertains to a monomer obtained from one or more of Formula I1 and a preferred formula thereof wherein one or both of R ³ and R ⁴ are a polymerizable group, or is obtained from A polymerizable liquid crystal mixture as defined above, a SCLCP by copolymerization or similar polymerization with one or more additional liquid crystal or non-liquid crystal comonomers.

A side chain liquid crystal polymer or copolymer (SCLCP) in which a component having semiconducting properties is positioned as a side group which is separated from the elastic skeleton by an aliphatic spacer group provides a highly ordered sheet The possibility of form. The structure consists of a tightly packed conjugated aromatic liquid crystal precursor, which can occur very tightly (usually less than 4) ) π-π stacking. This stacking enables intermolecular charge transfer to occur more easily, thereby achieving high charge carrier mobility. SCLCP can be advantageously used in certain applications because it can be readily synthesized prior to processing and subsequently processed, for example, from a solution in an organic solvent. If SCLCP is used in a solution, it can spontaneously align when applied to a suitable surface and when at its intermediate phase temperature, which can result in a large, highly ordered domain.

SCLCP can be derived from the present invention by the above methods or by conventional polymerization techniques known to those skilled in the art, including, for example, free radical, anionic or cationic chain polymerization, addition polymerization or polycondensation. Preparation of polymeric compounds or mixtures. The polymerization can be carried out, for example, as a polymerization reaction in a solution without coating or pre-alignment or as an in-situ polymerization. SCLCP can also be formed by grafting a compound of the invention having a suitable reactive group or a mixture thereof onto a pre-synthesized isotropic or anisotropic polymer backbone in a similar polymerization reaction. For example, a compound having a terminal hydroxyl group can be bonded to a polymer backbone having a pendant carboxylic acid or ester group, and a compound having a terminal isocyanate group can be added to a backbone having a free hydroxyl group, having a terminal vinyl group or ethylene. The oxy group compound can be added to, for example, a polyoxyalkylene skeleton having a Si-H group. SCLCP can also be formed from the compounds of the invention, as well as conventional liquid crystal or non-liquid crystal comonomers, by copolymerization or similar polymerization. Suitable comonomers are well known to those skilled in the art. In principle, it is possible to use all known copolymers known in the art with a reactive or polymerizable group capable of undergoing the desired polymer formation reaction, such as a polymerizable or reactive P group as described above. Typical liquid crystal raw comonomers are exemplified by WO 93/22397, European Patent No. 0 261 712, German Patent No. 195 04 224, WO 95/22586, WO 97/00600 and British Patent No. 2 351 734. Mentioned in the number. Typical non-liquid crystal raw comonomers are, for example, alkyl acrylates or alkyl methacrylates containing an alkyl group of 1 to 20 C atoms, for example, methyl acrylate or methyl methacrylate.

The monomers, oligomers and polymers of the present invention are useful as optical, electronic, and semiconductor materials, particularly as charge transfer materials in field effect transistors (FETs), for example, as integrated circuits, ID tags, or Components in TFT applications. Alternatively, it can be used in organic light emitting diodes (OLEDs) in electroluminescent display applications or as backlights for, for example, liquid crystal displays, as photovoltaic materials or sensor materials, for electrophotographic recording And for other semiconductor applications.

In particular, the oligomers and polymers of the present invention exhibit preferred solubility properties which allow for the production process to employ solutions of such compounds. Thus, films (including layers and coatings) can be formed by low cost manufacturing techniques such as spin coating. Suitable solvents or solvent mixtures include alkanes and/or aromatic compounds, especially fluorinated derivatives thereof.

The materials of the present invention are useful as optical, electronic, and semiconductor materials, particularly as charge transfer materials in field effect transistors (FETs), as photovoltaic materials or sensor materials, for electrophotographic recording, And for other semiconductor applications. The FETs, wherein one of the organic semiconducting materials is disposed as a thin film between the gate dielectric layer and a drain and a source electrode, is generally available, for example, from U.S. Patent No. 5,892,244 and WO 00/79617. U.S. Patent No. 5,998,804, and the references cited in the "Technical" and prior art sections and the references listed below. Since the solubility properties of the compounds of the present invention can have a number of advantages (such as low production costs) and the resulting large surface treatability, preferred applications of such FETs are, for example, integrated circuits, TFT- Display and security applications.

An inventive OFET device preferably comprises: - a source electrode, - a drain electrode, - a gate electrode, - a semiconductor layer, - one or more gate insulator layers, - a substrate as appropriate.

Wherein the semiconducting layer comprises a compound of formula I.

The OFET device can be a top gate device or a bottom gate device. Suitable structures and methods of manufacture for an OFET device are known to those skilled in the art and are described, for example, in WO 03/052841.

In safety applications, field effect transistors and other devices using semiconductor materials (such as transistors or diodes) can be used for ID tags or security tags to prove or prohibit the copying of value documents such as bank notes, credit cards or ID cards, Country ID file, license or any product of monetary value, such as stamps, tickets, stocks, checks, etc.

Alternatively, the monomers, oligomers, and polymers of the present invention can be used, for example, in organic light-emitting devices or diodes (OLEDs) in display applications or as backlights for, for example, liquid crystal displays. Commonly used OLEDs are achieved using a multilayer structure. An emissive layer is typically sandwiched between one or more electron transfer layers and/or hole transfer layers. Electrons and holes as charge carriers can be moved toward the emissive layer by application of a voltage and recombined there to excite the luminophore units contained in the emissive layer and thereby cause the units to emit light. The compounds, materials and films of the present invention can be used in one or more charge transport layers and/or emissive layers depending on their electrical and/or optical properties. Moreover, it is particularly advantageous if the compounds, materials and films of the invention exhibit electroluminescent properties by themselves or comprise electroluminescent groups or compounds. The selection, characterization, and processing of suitable monomers, oligomers, and polymeric compounds or materials for use in OLEDs are well known to those skilled in the art, see, for example, Meerholz in Synthetic Materials (111-112, 2000). , 31-34), Alcala is described in J. Appl. Phys. (88, 2000, 7124-7128) and in the documents cited therein.

According to another use, the compounds, materials or films of the invention (especially those exhibiting photoluminescent properties) can be used, for example, as light source materials for display devices, for example in European Patent No. 0 889 350 A1 or C. Weder et al. are described in Science (279, 1998, 835-837).

Depending on the other use, the compounds, materials or films of the present invention may be used alone or in combination with other materials in an LCD or OLED device or as an alignment layer therein, as described, for example, in U.S. Patent No. 2003/0021913. The conductivity of the alignment layer can be increased by using the charge transfer compound of the present invention. When used in an LCD, this increased conductivity can reduce the adverse residual DC effects in the switchable LCD unit and suppress image sticking or reduce the spontaneous polarity of the switched ferroelectric LC in, for example, a ferroelectric LCD. The residual charge generated by the charge. When used in an OLED device comprising a luminescent material that is provided on an alignment layer, this increased conductivity enhances the electroluminescent properties of the luminescent material. The compound or material of the present invention having liquid crystallinity or liquid crystal properties can form an anisotropically oriented film as described above, which is particularly useful as an alignment layer to initiate or enhance a liquid crystal medium (which is provided on the anisotropic film) In the alignment. The materials of the present invention may also be used in combination with a photoisomerizable compound and/or a chromophore or as a photoalignment layer, as described in U.S. Patent No. 2003/0021913.

According to another use, the polymers of the invention, especially water-soluble derivatives thereof, such as those having polar or ionic side chain groups; or ion doped forms, can be used as chemical sensors or materials for detection and identification. DNA sequence. For such uses see, for example, L. Chen, DW McBranch, H. Wang, R. Helgeson, F. Wudl and DGW Hiten in Proc. Natl. Acad. Sci. USA 1999, 96, 12287, D. Wang, X. .Gong, PS Heeger, F. Rininsland, GC Bazan and AJ Heeger in Proc. Natl. Acad. Sci. USA 2002, 99, 49, N. DiCesare, MR Pinot, KSSchanze and JRLakowicz in Langmuir 2002, 18, 7785, DTMcQuade, AEPullen, TMSwager, in Chem. Rev. 2000, 100, 2537.

The following examples are intended to illustrate the invention and are not intended to limit the invention. Above and below, all temperatures are given in degrees Celsius, and all percentages are by weight unless otherwise indicated.

Example 1

Poly(3-mercaptothieno[2,3-b]thiophene-2,5-diyl) (1) was prepared as follows.

1-(Thien-2-ylthio)-dodecan-2-one: To a solution of monothiophene-2-thiol (2.0 g, 17.2 mmol) dissolved in anhydrous acetone (100 mL) Potassium carbonate (2.8 g; 20 mmol) followed by 1-chlorododecan-2-one (3.8 g, 17.2 mmol). The reaction was stirred for 30 minutes, filtered at rt and concentrated under reduced pressure. The crude product was further purified by column chromatography (EtOAc:EtOAc:EtOAc:EtOAc M/Z 298 (M ⁺ ). ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.36 (1H, dd), 7.15 (1H, dd), 6.96 (1H, dd), 3.55 (2H, s), 2.55 (2H, t), 1.57 (2H, m), 1.35-1.20 (14H, m), 0.88 (3H, t). ^{1 3} C NMR (75 MHz, CDCl ₃ ) δ 205.1, 134.6, 132.5, 130.3, 127.7, 48.2, 41.1, 31.9, 29.6, 29.5, 29.4, 29.3, 29.1, 23.8, 22.7, 14.1.

3-mercapto-thieno[2,3-b]thiophene: a 4-(thiophen-2-ylthio)-dodecan-2-one via a 4A molecular sieve (Soxhlet) (3.40 g, 11.4 mmol) The ear and amberlyst 15 (5.5 g) were dissolved in chlorobenzene (200 mL) and heated to reflux for 16 hours. The reaction was cooled, filtered and concentrated under reduced pressure. The resulting residue was dissolved in gasoline and filtered through a small ceria column to remove colored impurities. The organics were concentrated under reduced pressure and further purified by column chromatography eluting with EtOAc (EtOAc:EtOAc). The first part was collected to give a colorless oily product (1.8 g, 56%). M/Z 280 (M ⁺ ). ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.34 (1H, dd), 7.18 (1H, d), 6.93 (1H, d), 2.75 (2H, t), 1.70 (2H, quint), 1.40-1.20 ( 14H, m), 0.88 (3H, t). ^{1 3} C NMR (75 MHz, CDCl ₃ ) δ 147.3, 136.9, 135.1, 127.8, 122.4, 119.0, 31.9, 29.8, 29.65, 29.63, 29.50, 29.49 (2C), 29.4, 22.7, 14.2.

2,5-Dibromo-3-dodecylthieno[2,3-b]thiophene: 5 parts of an equivalent of 3-mercaptothieno[2,3-b at 0 ° C for 30 minutes N-bromosuccinimide (1.98 g, 11.1 mmol) was added to a solution of thiophene (1.50 g, 5.35 mmol) in THF (20 mL). The reaction was stirred at room temperature for 72 hours. Another portion of NBS (0.2 g, 1.1 mmol) was added and the mixture was stirred for an additional hour. The solvent was removed under low pressure, the residue was dissolved in ethyl acetate (50 mL) and washed with water (2 x 25 mL) and brine (2 x 25 mL), dried (Na ₂ SO _4), filtered and Concentrated at low pressure. The residue was suspended in gasoline and filtered through a ceria core column and eluted with petrol. The organics were concentrated under reduced pressure to give a colourless oil (yield: <RTIgt; M/Z 436 (M ⁺ , 2%), 438 (M ⁺ , 4%), 440 (M ⁺ , 2%). ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.14 (1H, s), 2.69 (2H, t), 1.59 (2H, quint), 1.40-1.20 (14H, m), 0.88 (3H, t). ^{1 3} C NMR (75 MHz, CDCl ₃ ) δ 114.6, 134.5, 134.0, 122.2, 113.0, 110.0, 31.9, 26.93, 29.58, 29.44, 29.36 (2C), 29.0, 28.8, 22.7, 14.2. Elemental analysis for C _{1 6} H _{2 2} Br ₂ S ₂ : calcd for C, 43.85; Experimental value C, 43.5; H, 5.1.

Poly(3-mercaptothieno[2,3-b]thiophene-2,5-diyl): a 2,5-dibromo-3-indolylthieno[2,3-b at 0 °C Add a solution of thiophene (0.88 g, 2 mmol) dissolved in anhydrous THF (10 mL) with diisopropylmagnesium bromide (1.02 mL of a solution of 2.0 M in diethyl ether, 2.04 mmol) in. The reaction was warmed to room temperature and stirred at this temperature for 1 hour. An aliquot of the reaction mixture was quenched with water and the organic extract was analyzed by GCMS to show that 98% of the mono-grid product was formed in a 9:1 isomer ratio. Now a portion of the solid was added Ni (dppf) Cl ₂ (28.0 mg, 2 mole%), and was at 160 ℃ The reaction was heated for 20 min at a microwave reactor (Emrys Creator, Personal Chemistry) in. The reaction was cooled, poured into methanol and stirred 1 hr. The resulting precipitate was filtered and washed with additional methanol, acetone and hexanes. The resulting brown powder was dissolved in chloroform and precipitated into a methanol solution and dried to give a red powder (235 mg). GPC (chlorobenzene) Mn 7,500 g / mol; Mw 20,000 g / mol. λ _{m a x} 320,368,382 (sh) nanometer (film). ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.28 (br s, 1H), 2.96 (brm, 1.6H), 2.85 (brm, 0.4H), 1.68 (brm, 2H), 1.45 - 1. m, 18H), 0.86 (br t, 3H) (Note: The positional regularity is estimated to be between 80 and 85%. The measurement is difficult because the low molecular weight of the polymer can cause interference from the end groups. And because protons adjacent to the skeleton may not be easily resolved due to aggregation effects).

Example 2

Poly(3,4-di-dodecyl-thieno[2,3-b]thiophene) (2) was prepared as follows.

2,3,4,5-tetrabromo-thieno[2,3-b]thiophene: to a thieno[2,3-b]thiophene (0.74 g, 5.3 mmol) dissolved in acetic acid (60 ml) Bromine (2 mL, 39 mmol) was added to the solution. The reaction was heated to reflux for 1.5 h. After cooling, an aqueous solution of sodium sulfite (10% w/v) was added until the color of excess bromine disappeared. The reaction mixture was extracted with dichloromethane, washed with saturated aqueous sodium carbonate solution, dried (Na ₂ SO _4), filtered and concentrated under reduced pressure. The product was purified by recrystallization from hot methanol / methylene chloride to afford fine pale yellow needles (1.59 g, 66%). M/Z (455, quintuple, M ⁺ ). Found: C, 16.1; Br, 69.7. Calculated for C ₆ Br ₄ S ₂ : C, 15.8; Br 70.1. The desired signal can be obtained by NMR.

3,4-dibromo-thieno[2,3-b]thiophene: a 2,3,4,5-tetrabromothieno[2,3-b]thiophene (0.83 g, 1.8 mmol), A mixture of zinc powder (0.29 g, 4.4 mmol) and acetic acid (30 mL) was heated to reflux for 2 h. The reaction mixture was poured into water and extracted with DCM, washed with saturated aqueous sodium carbonate, dried (Na ₂ SO ₄₎ and concentrated under reduced pressure. The product was purified by recrystallization from hot methanol to afford white crystals (yield: 389 mg, 72%). M/Z (298, t, M ⁺ ). Found: C, 24.5; H, 0.8. Calculated C ₆ H ₂ Br ₂ S ₂ values of: C, 24.2; H, 0.7 . ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.32 (s, 2H). ^{1 3} C NMR (300 MHz, CDCl ₃ ) δ 139.35, 137.42, 126.44, 102.96.

3,4-di-dodecyl-thieno[2,3-b]thiophene: a microwave vial was charged with 3,4-dibromo-thieno[2,3-b]thiophene (1.02 g, 3.42 mmol, Pd(dppf)Cl ₂ (57 mg, 0.09 mmol), sealed and purged with nitrogen. Anhydrous tetrahydrofuran (2 ml) was added followed by additional dodecylzinc bromide (16.8 ml of 0.5 M in THF, 8.4 mmol) and the reaction mixture was stirred at room temperature for 10 min then in microwave Heat at 150 ° C for 7 minutes. The reaction mixture was poured into a dilute aqueous solution of hydrochloric acid and extracted with dichloromethane. Organics were washed with water (until a pH of about 7), dried (Na ₂ SO _4), filtered and concentrated under reduced pressure. The product was purified by column chromatography on silica gel eluting with petrol (40 to 60 ° C) and then recrystallized from hot methanol / dichloromethane to give fine white needles (666 mg, 41 %). M/Z 476 (M ⁺ ). Found: C, 75.5; H, 11.0; S, 14.2. C _{3 0} H _{5 2} S ₂ calculated values of: C, 75.6; H, 11.0 ; S, 13.4. ¹ H NMR (300 MHz, CDCl ₃ ) δ 6.90 (s, 2H), 2.82 (t, 4H, J = 7.8 Hz), 1.69 (quint, 4H), 1.43 (m, 4H), 1.27 (m, 36H) , 0.88 (t, 6H, J = 6.6 Hz). ^{1 3} C NMR (300 MHz, CDCl ³ ) δ 145.21, 137.85, 136.06, 122.30, 31.94, 30.36, 29.70, 29.67, 29.65, 29.58, 29.55, 29.44, 29.38, 22.70, 14.11.

Poly(3,4-di-dodecyl-thieno[2,3-b]thiophene) (2): Dissolved in a stirred solution of ferric chloride (300 mg, 1.84 mmol) in chloroform (50 ml) A solution of 3,4-di-dodecyl-thieno[2,3-b]thiophene (206 mg, 0.43 mmol) dissolved in chloroform (5 mL) was added dropwise. The reaction was stirred at room temperature for 48 hours while bubbling into the reaction mixture with a constant stream of nitrogen to remove the formed hydrochloric acid. The dark blue residue was dissolved in a concentrated solution of chloroform to precipitated methanol (300 ml). The resulting precipitate was filtered and washed with methanol. The material was removed by stirring in a concentrated aqueous ammonia solution (100 mL, 33%) for 1 hour, filtered, washed with water and then with methanol to afford a brown solid. The polymer was washed and extracted with methanol for 18 hours with Soxhlet and then with acetone for 18 hours. The polymer was dissolved in chloroform and crystallised eluted eluted elute GPC (chlorobenzene) Mn (9,600 g/mole), Mw (34,000 g/mole). λ _{m a x} 320 nm (chloroform). λ _{m a x} 330 nm (film). ¹ H NMR NMR (300 MHz, C ₆ D ₄ Cl ₂ , 50 ° C) δ 2.7-2.4 (v.br s, 4H), 1.65-1.1 (brm, 40h), 0.89 (br s, 6H).

Example 3

Poly(3,4-di-dodecyl-thieno[2,3-b]thiophene-2,5-diyl-co-thieno[2,3-b]thiophene-2,5-diyl -) (3) was prepared as follows.

2,5-Dibromo-3,4-di-dodecylthieno[2,3-b]thiophene: to a 3,4-di-dodecylthieno[2,3-b]thiophene (0.316 g, 0.75 mmol) EtOAc (EtOAc) (EtOAc) An aqueous solution of sodium sulfite (10% w/v) was added until the color of excess bromine disappeared. The reaction mixture was extracted with dichloromethane, washed with saturated aqueous sodium carbonate solution, dried (Na ₂ SO ₄₎ and concentrated under reduced pressure. The product was purified by column chromatography eluting with EtOAc (EtOAc (EtOAc) (Calculated value: C, 55.9; H, 8.0; Br, 25.2; S, 9.5. Calculated for C _{3 0} H _{5 0} Br ₂ S ₂ : C, 56.8; H, 7.9; Br, 25.2; S, 10.1) ¹ H NMR (300 MHz, CDCl ₃ ) δ 2.75 (t, 4H, J = 7.93 Hz), 1.55 (5 s, 4H, ), 1.42 (m, 4H), 1.27 (m, 32H), 0.88 (t) , 6H, J = 6.95 Hz).

Poly(2-thieno[2,3-b]thiophen-2-yl-co-3,4-di-dodecyl-thieno[2,3-b]thiophene) (3): to dry The microwave tube is filled with 2,5-dibromo-3,4-di-dodecylthieno[2,3-b]thiophene (150 mg, 0.236 mmol), 2,5-double (three Methylstannyl)thieno[2,3-b]thiophene (110 mg, 0.236 mmol), hydrazine (dibenzylideneacetone) dipalladium (0) (4.3 mg, 4.7 micromolar), Tri-o-tolylphosphine (5.7 mg, 19 micromoles) and chlorobenzene (4.5 ml). The tube was sealed and degassed with nitrogen for 1 minute, then heated in a microwave at 140 ° C for 60 seconds, then at 160 ° C for 60 seconds, then at 180 ° C for 60 seconds, and finally at 200 ° C. Heat down for 600 seconds (fixed hold time). The reaction was cooled to 50 &lt;0&gt;C and then poured into MeOH (EtOAc) (EtOAc) The reaction was filtered through a soxhlet filter cannula, followed by extraction with acetone (soxhlet) for 72 hours, extraction with methanol for 8 hours, and extraction with gasoline (40 to 60 ° C) for 14 hours. The residue was dissolved in dichlorobenzene and precipitated to warm (50 &lt GPC (chlorobenzene) Mn 9,400 g/mole, Mw 28,000 g/mole (λ _{m a x} 327 nm (chloroform). λ _{m a x} 326, 374,398 (sh) nano (film). ¹ H NMR (300 MHz , CDCl ₃ , 50 ° C) δ 7.28 (br s, 2H), 2.99 (br s, 4H), 1.68 (br s, 4H), 1.45-1.1 (br m, 36H), 0.87 (t, 6H).

Claims (22)

a polymer selected from the group consisting of Wherein R ¹ and R ² are each independently C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -alkoxy, C ₁ -C ₂₀ -alkenyl, C ₁ -C ₂₀ -alkynyl, C ₁ - C ₂₀ -alkylthio, C ₁ -C ₂₀ -carboxyalkyl, C ₁ -C ₂₀ -ester, C ₁ -C ₂₀ -amino or C ₁ -C ₂₀ -fluoroalkyl, R ³ and R ⁴ Independently halogen, optionally substituted aryl or heteroaryl, or linear, branched or cyclic alkyl having 1 to 20 C atoms which may be unsubstituted, F, Cl, Br , I or CN may be mono- or poly-substituted, wherein one or more non-adjacent CH ₂ groups may also, in each case, independently pass through -O-, -S-, -NH-, -NR ⁰ -, - SiR ⁰ R ⁰⁰ -, -CO-, -COO-, -OCO-, -O-CO-O-, -S-CO-, -CO-S-, -CX ¹ =CX ² - or -C≡C a substitution, but the substitution is such that O and/or S atoms are not directly linked to each other, or represent -Sn(R ⁰ ) ₃ , -B(OR')(OR"), -CH ₂ Cl, -CHO, -CH =CH ₂ or -SiR ⁰ R ⁰⁰ R ⁰⁰⁰ , R ⁰ , R ⁰⁰ , R ⁰⁰⁰ are independently H, aryl or an alkyl group having 1 to 12 C atoms, and R' and R" are independently H Or an alkyl group having 1 to 12 C atoms, or OR' and OR" together with a boron atom to form a C atom having 2 to 10 Cycloalkyl group, X ¹ and X ² are each independently based H, F, Cl or CN, n lines from a integer from 10 to 5000, and m lines n / 2. The polymer of claim 1, wherein R ¹ and R ² are selected from the group consisting of C ₁ -C ₂₀ -alkyl or C ₁ -C ₂₀ -fluoroalkyl. The polymer of claim 1 or 2, wherein R ³ and R ⁴ are selected from the group consisting of halogen, -Sn(R ⁰ ) ₃ , -B(OR')(OR"), -CH ₂ Cl, -CHO, -CH =CH ₂ or -SiR ⁰ R ⁰⁰ R ⁰⁰⁰ and optionally substituted aryl or heteroaryl. Use of a polymer according to any one of claims 1 to 3 as a semiconductor or charge transfer material for use in optical, optoelectronic or electronic devices, for use in optical, optoelectronic or electronic devices, as In a field effect transistor (FET) of an integrated circuit component Thin film transistors (TFTs) for flat panel display applications, liquid crystal displays (LCDs), for radio frequency identification (RFID) tags, for displays or organic light-emitting diodes ( In a semiconductor component of an organic light emitting diode; OLED), used in a photovoltaic device or a sensor device, used as an electrode material in a battery, as a photoconductor, used in an electrophotographic application such as electrophotographic recording For organic memory devices. A semiconductor material comprising at least one polymer according to any one of claims 1 to 3. A charge transporting material comprising at least one polymer of any one of claims 1 to 3. A FET comprising the polymer of any one of claims 1 to 3. An integrated circuit (IC) comprising the polymer of any one of claims 1 to 3. A TFT comprising the polymer of any one of claims 1 to 3. An OLED comprising the polymer of any one of claims 1 to 3. A TFT array for a flat panel display, comprising the FET of claim 7, the IC of claim 8, the TFT of claim 9, or the OLED of claim 10. A radio frequency identification (RFID) tag comprising a FET as claimed in claim 7, an IC such as claim 8, an TFT such as claim 9, or an OLED as claimed in claim 10. An electroluminescent display comprising a FET as claimed in claim 7, an IC such as claim 8, an TFT such as claim 9, or an OLED as claimed in claim 10. A backlight comprising a FET as claimed in claim 7, an IC such as claim 8, an TFT such as claim 9, or an OLED as claimed in claim 10. A security token comprising a FET as claimed in item 7 or an RFID tag as in claim 12. A security device comprising a FET as claimed in claim 7 or an RFID tag as in claim 12. The polymer of claim 1 or 2 which is oxidized or reductively doped to form a conductive ionic species. A charge injection layer comprising the polymer of claim 17. A planarization layer comprising the polymer of claim 17. An antistatic film comprising the polymer of claim 17. A conductive substrate comprising the polymer of claim 17. A conductive pattern comprising the polymer of claim 17.